WO2022249866A1 - Composition de bêta-myrcène ainsi que procédé de production de polymère mettant en oeuvre cette composition de bêta-myrcène - Google Patents

Composition de bêta-myrcène ainsi que procédé de production de polymère mettant en oeuvre cette composition de bêta-myrcène Download PDF

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WO2022249866A1
WO2022249866A1 PCT/JP2022/019596 JP2022019596W WO2022249866A1 WO 2022249866 A1 WO2022249866 A1 WO 2022249866A1 JP 2022019596 W JP2022019596 W JP 2022019596W WO 2022249866 A1 WO2022249866 A1 WO 2022249866A1
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myrcene
composition
peak
polymerization
substance group
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PCT/JP2022/019596
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Japanese (ja)
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泰政 後藤
伶奈 児島
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デンカ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/22—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having three or more carbon-to-carbon double bonds

Definitions

  • the present invention relates to a ⁇ -myrcene composition having a low content of polymerization inhibitors and improved initiator efficiency in anionic polymerization, and a method for producing a polymer using the ⁇ -myrcene composition.
  • An object of the present invention is to provide a ⁇ -myrcene composition having a low content of polymerization inhibitors and improved initiator efficiency in anionic polymerization, and a method for producing a polymer using the ⁇ -myrcene composition. .
  • the present invention (1) In the gas chromatography analysis under the following conditions, The area ratio of the ⁇ -myrcene peak is 75% or more, When the relative retention time of the ⁇ -myrcene peak is set to 1.0, The area ratio of the peak of substance group 1 appearing in the range of relative retention time 1.29 to 1.78 is 1000 ppm or less, ⁇ -myrcene compositions.
  • Components corresponding to substance group 1 include L-pinocarbeol, pinene oxide, L-perillaldehyde, peryl alcohol, (4-isopropyl-1,3-cyclohexadien-1-yl)methanol, and dibutyl
  • the ⁇ -myrcene composition according to any one of (1) to (4), containing one or more selected from the group consisting of hydroxytoluene.
  • the area ratio of the peak of substance group 2 appearing in the range of relative retention time 1.10 to 1.29 is 10000 ppm or less, and the component corresponding to substance group 2 is 5-ethyldiene-1-methylcyclo.
  • ⁇ -myrcene composition containing one or more selected from the group consisting of ptene, (4E,6Z)-2,6-dimethyl-2,4,6-octatriene, and 3,4-dimethyl-2,4,6-octatriene;
  • the ⁇ -myrcene composition according to any one of (1) to (5).
  • the area ratio of the peak of substance group 3 appearing in the range of relative retention time 1.78 to 2.45 is 6000 ppm or less, and the component corresponding to substance group 3 is 2, 6, 11, 15- Tetramethylhexadeca-2,6,8,10,14-pentaene, 2,6,11,15-tetramethyl-2,6,8,10,14-hexadecapentaene, 2,6,8,10 , 14-hexadecapentene-1,6,11,15-tetramethyl, 5-(5-methyl-1-methylene-4-hexene-1-yl)-1-(4-methyl-3-pentene- 1-yl), 4-(5-methyl-1-methylene-4-hexen-1-yl)-1-(4-methyl-3-penten-1-yl), 5-ethynyl-1,5-bis (4-methyl-3-penten-1-yl), 4-ethynyl-1,4-bis(4-methyl-3-penten-1-yl), including one or more selected from the group consist
  • the area ratio of the peak of substance group 4 appearing in the range of relative retention time 0.00 to 0.49 is 1000 ppm or less, and the components corresponding to substance group 4 include 1-butene, 2-butene, ( The ⁇ -myrcene composition according to any one of 1) to (7). (9) A method for producing a polymer, comprising the step of polymerizing the ⁇ -myrcene composition according to any one of (1) to (8). (10) The ⁇ -myrcene composition according to any one of (1) to (8) is combined with an aromatic vinyl hydrocarbon-based monomer, or a conjugated diene-based monomer other than the aromatic vinyl hydrocarbon-based monomer and ⁇ -myrcene.
  • a method of making a copolymer comprising the step of copolymerizing with (11)
  • the ⁇ -myrcene composition according to any one of (1) to (8) is combined with an aromatic vinyl hydrocarbon-based monomer or a conjugated diene-based monomer other than the aromatic vinyl hydrocarbon-based monomer and ⁇ -myrcene.
  • a to B means A or more and B or less.
  • PaA is the unit of absolute pressure
  • Pa is the unit of gauge pressure.
  • ⁇ -myrcene> ⁇ -myrcene is a natural product, and the purity of ⁇ -myrcene as a raw material generally distributed is often about 70%. In addition, the purity of ⁇ -myrcene generally includes structural isomers of ⁇ -myrcene in many cases.
  • the purity of ⁇ -myrcene in the present invention means the purity of a single ⁇ -myrcene product that does not contain structural isomers of ⁇ -myrcene.
  • the purity of ⁇ -myrcene in the present invention is obtained as the area ratio of the ⁇ -myrcene peak in gas chromatography analysis under the conditions described later.
  • the ⁇ -myrcene composition according to the present embodiment has a ⁇ -myrcene peak area ratio of 75% or more, preferably 78% or more, and more preferably 80% or more in gas chromatography analysis under the conditions described later. be.
  • the area ratio of the ⁇ -myrcene peak is, for example, 75, 80, 85, 90, 95, 99%, and may be within a range between any two of the numerical values exemplified here. .
  • the area ratio of the ⁇ -myrcene peak in the ⁇ -myrcene composition is 75% or more, the content of polymerization inhibitors in the ⁇ -myrcene composition is reduced, and the initiator efficiency in anionic polymerization is improved.
  • Examples of the method for making the ⁇ -myrcene peak area ratio of the ⁇ -myrcene composition 75% or more include distillation purification of ⁇ -myrcene as a raw material.
  • the ⁇ -myrcene composition according to the present embodiment has a relative retention time of 1.29 to 1.78 when the relative retention time of the ⁇ -myrcene peak is 1.0 in the gas chromatography analysis under the conditions described later. is 1000 ppm or less, preferably 800 ppm or less, more preferably 500 ppm or less, and still more preferably 300 ppm or less.
  • the area ratios of the peaks of Substance Group 1 are, for example, 1, 10, 100, and 1000 ppm, and may be within a range between any two of the numerical values exemplified here.
  • the peak area ratio of substance group 1 in the ⁇ -myrcene composition is 1000 ppm or less, the content of polymerization inhibitors in the ⁇ -myrcene composition is reduced, and the initiator efficiency in anionic polymerization is improved.
  • a method for making the peak area ratio of the substance group 1 of the ⁇ -myrcene composition 1000 ppm or less for example, ⁇ -myrcene as a raw material is purified by distillation.
  • the ⁇ -myrcene composition according to the present embodiment contains L-pinocarveol, pinene oxide, L-perillaldehyde, peryl alcohol, (4-isopropyl-1,3-cyclohexadiene-1 -yl) methanol, and one or more selected from the group consisting of dibutylhydroxytoluene.
  • the peak area ratio of the component corresponding to the substance group 1 in the ⁇ -myrcene composition is 1000 ppm or less, the content of polymerization inhibitors in the ⁇ -myrcene composition is reduced, and the initiator efficiency in anionic polymerization is improved. do.
  • Examples of the method for making the peak area ratio of the component corresponding to the above substance group 1 in the ⁇ -myrcene composition 1000 ppm or less include distillation purification of ⁇ -myrcene as a raw material.
  • the peak area ratio of the components corresponding to substance group 1 is the total peak area ratio of the components corresponding to substance group 1 .
  • the mechanism by which the initiator efficiency is improved by controlling the peak area ratio of the component corresponding to substance group 1 to 1000 ppm or less is unknown. If the ⁇ -myrcene composition contains a large amount of the polymerization inhibitor or oxygen-containing compound, the polymerization inhibitor or oxygen-containing compound reacts with the active terminal in the anionic polymerization, and deactivates the active species.
  • the ⁇ -myrcene composition according to the present embodiment has a relative retention time of 1.10 to 1.29 when the relative retention time of the ⁇ -myrcene peak is 1.0 in the gas chromatography analysis under the conditions described later. is preferably 10000 ppm or less, more preferably 8000 ppm or less, still more preferably 5000 ppm or less, and still more preferably 3000 ppm or less.
  • the peak area ratio of substance group 2 is, for example, 1, 10, 100, 1000 and 10000 ppm, and may be within a range between any two of the numerical values exemplified here.
  • the peak area ratio of substance group 2 in the ⁇ -myrcene composition is 10000 ppm or less, the content of polymerization inhibitors in the ⁇ -myrcene composition is reduced, and the initiator efficiency in anionic polymerization is improved.
  • a method for making the peak area ratio of the substance group 2 of the ⁇ -myrcene composition 10000 ppm or less for example, ⁇ -myrcene as a raw material is purified by distillation.
  • the ⁇ -myrcene composition according to the present embodiment contains 5-ethyldiene-1-methylcycloheptene and (4E,6Z)-2,6-dimethyl-2,4,6-octatriene as components corresponding to substance group 2. , 3,4-dimethyl-2,4,6-octatriene.
  • the peak area ratio of the component corresponding to the substance group 2 described above in the ⁇ -myrcene composition is 10000 ppm or less, the content of polymerization inhibitors in the ⁇ -myrcene composition is reduced, and the initiator efficiency in anionic polymerization is improved. do.
  • Examples of the method of making the peak area ratio of the component corresponding to the substance group 2 in the ⁇ -myrcene composition 10000 ppm or less include distillation purification of ⁇ -myrcene as a raw material.
  • the peak area ratio of the components corresponding to substance group 2 is the total peak area ratio of the components corresponding to substance group 2 .
  • the mechanism by which the initiator efficiency is improved by controlling the area ratio of the peak of the component corresponding to substance group 2 to 10000 ppm or less is unknown, but it is considered as follows. be done. That is, when a large amount of group D monomers corresponding to substance group 2 are contained in the ⁇ -myrcene composition, group D monomers preferentially react in anionic polymerization to generate active terminals, but then group A monomers, ⁇ Although it cannot react with myrcene and the reaction stops, it is thought that the reaction is prevented from stopping by keeping the content of such D group monomers at 10000 ppm or less.
  • the A group monomers and D group monomers referred to herein refer to the fact that the reactivity of vinyl monomers in anionic polymerization greatly depends on the resonance effect due to conjugation and the strength of the electron-withdrawing properties of the substituents. Anion It is based on the theory of systematically combining combinations with polymerizable monomers.
  • ⁇ -myrcene corresponds to the A group monomer
  • an initiator belonging to the a group is selected.
  • the active terminal is included in the ⁇ -myrcene composition.
  • D group monomers It is believed to preferentially react with the contained D group monomers. It is considered that the active terminal produced from the D group monomer has low reactivity with myrcene, which is the A group monomer, and thus the reaction has stopped. In the present embodiment, it is considered that stopping the reaction is prevented by keeping the content of the group D monomer corresponding to the substance group 2 below a predetermined amount.
  • the ⁇ -myrcene composition according to the present embodiment has a relative retention time of 1.78 to 2.45 when the relative retention time of the ⁇ -myrcene peak is 1.0 in gas chromatography analysis under the conditions described later. is preferably 6000 ppm or less, more preferably 4000 ppm or less, still more preferably 2000 ppm or less, still more preferably 1000 ppm or less.
  • the area ratios of the peaks of substance group 3 are, for example, 1, 10, 100, 1000 and 6000 ppm, and may be within a range between any two of the numerical values exemplified here.
  • the peak area ratio of substance group 3 in the ⁇ -myrcene composition is 6000 ppm or less, the content of polymerization inhibitors in the ⁇ -myrcene composition is reduced, and the initiator efficiency in anionic polymerization is improved.
  • a method for making the peak area ratio of substance group 3 of the ⁇ -myrcene composition 6000 ppm or less for example, ⁇ -myrcene as a raw material is purified by distillation.
  • the ⁇ -myrcene composition according to the present embodiment contains 2,6,11,15-tetramethylhexadeca-2,6,8,10,14-pentaene, 2,6,11 as components corresponding to substance group 3.
  • the peak area ratio of the component corresponding to the substance group 3 described above in the ⁇ -myrcene composition is 6000 ppm or less, the content of polymerization inhibitors in the ⁇ -myrcene composition is reduced, and the initiator efficiency in anionic polymerization is improved. do.
  • Examples of the method of making the peak area ratio of the component corresponding to the substance group 3 in the ⁇ -myrcene composition 6000 ppm or less include distillation purification of ⁇ -myrcene as a raw material.
  • the peak area ratio of the components corresponding to substance group 3 is the total peak area ratio of the components corresponding to substance group 3 .
  • the mechanism by which the initiator efficiency is improved by controlling the peak area ratio of the component corresponding to substance group 3 to 6000 ppm or less is unknown, but it corresponds to substance group 3. If a large amount of the ⁇ -myrcene dimer component is contained in the ⁇ -myrcene composition, the polymerization termination mechanism due to the ⁇ -myrcene dimer component will proceed in the anionic polymerization, and the polymerization initiator efficiency will decrease. Conceivable.
  • the ⁇ -myrcene composition according to the present embodiment has a relative retention time of 0.00 to 0.49 when the relative retention time of the ⁇ -myrcene peak is 1.0 in the gas chromatography analysis under the conditions described later. is preferably 1000 ppm or less, more preferably 800 ppm or less, still more preferably 500 ppm or less, and still more preferably 300 ppm or less.
  • the peak area ratios of the substance group 4 are, for example, 1, 300, 500, 800, and 1000 ppm, and may be within the range between any two of the numerical values exemplified here.
  • the area ratio of the peak of substance group 4 in the ⁇ -myrcene composition is 1000 ppm or less, the content of polymerization inhibitors in the ⁇ -myrcene composition is reduced, and the initiator efficiency in anionic polymerization is improved.
  • a method for making the peak area ratio of substance group 4 of the ⁇ -myrcene composition 1000 ppm or less for example, ⁇ -myrcene as a raw material is purified by distillation.
  • the ⁇ -myrcene composition according to the present embodiment contains 1-butene, 2-butene, 1,4-pentadiene, 2,4-hexadiene, 4-methyl-1,3-pentadiene, It may contain one or more selected from the group consisting of 4-methylcyclopentadiene and 4-methyl-1-methylenecyclohexane.
  • the peak area ratio of the component corresponding to substance group 4 in the ⁇ -myrcene composition is 1000 ppm or less, the content of polymerization inhibitors in the ⁇ -myrcene composition is reduced, and the initiator efficiency in anionic polymerization is improved. do.
  • the peak area ratio of the component corresponding to the substance group 4 in the ⁇ -myrcene composition 1000 ppm or less for example, ⁇ -myrcene as a raw material is purified by distillation.
  • the peak area ratio of the components corresponding to substance group 4 is the total peak area ratio of the components corresponding to substance group 4 .
  • the mechanism by which the initiator efficiency is improved by controlling the area ratio of the peak of the component corresponding to substance group 4 to 1000 ppm or less is unknown, but it corresponds to substance group 4. If the ⁇ -myrcene composition contains a large amount of the low boiling point component, the termination mechanism of polymerization due to the low boiling point component proceeds in the anionic polymerization, and the polymerization initiator efficiency is reduced.
  • the ⁇ -myrcene composition according to the present embodiment is subjected to gas chromatography analysis under the following conditions to obtain the content of the component contained in the ⁇ -myrcene composition as the peak area ratio of each component.
  • the gas chromatograph mass spectrometry is measured under the same conditions as the measurement conditions of the gas chromatography, such as the temperature rising conditions of the column, the peak with the same retention time as the peak qualitatively attributed to myrcene is also derived from myrcene in the gas chromatography analysis. It can be qualitatively determined that the peak Examples of the gas chromatograph mass spectrometer include GCMS-QP2020 NX manufactured by Shimadzu Corporation.
  • Substance group 2 The retention time of the ⁇ -myrcene peak identified as described above is defined as a relative retention time of 1.0, and peaks appearing in the range of relative retention times of 1.10 to 1.29 are defined as substance group 2 peaks. stipulate.
  • Substance group 3 The retention time of the ⁇ -myrcene peak identified as described above is defined as a relative retention time of 1.0, and peaks appearing in the range of relative retention times of 1.78 to 2.45 are defined as substance group 3 peaks. stipulate.
  • Substance group 4 The retention time of the ⁇ -myrcene peak identified as described above is defined as a relative retention time of 1.0, and the peaks appearing in the range of relative retention times of 0.00 to 0.49 are defined as the peaks of Substance Group 4. stipulate.
  • the ⁇ -myrcene composition according to the present embodiment is obtained, for example, by distilling and refining the ⁇ -myrcene raw material composition.
  • the distillation method is not particularly limited, for example, the ⁇ -myrcene raw material composition is placed in a vessel equipped with a distillation column, heated, and distilled under reduced pressure. By removing a predetermined amount of the initial distillation, the substance group 4 is removed, and then part of the distillate is recovered as a refined product. The amount remaining in the reaction vessel becomes a residue, and by leaving a predetermined amount of residue, substance group 1, substance group 2, and substance group 3 can be efficiently removed.
  • the distillation temperature is from 40°C to 150°C. If the distillation temperature is 40° C. or less, the distillation rate becomes slow, which is disadvantageous in terms of production efficiency. Dimerization of ⁇ -myrcene occurs at distillation temperatures above 150°C. As a result, the ratio of high-boiling components in the raw material ⁇ -myrcene increases, and the boiling point rises, making it difficult to distill ⁇ -myrcene, which is disadvantageous in that the yield of ⁇ -myrcene decreases.
  • the distillation pressure is preferably equal to or lower than the vapor pressure of ⁇ -myrcene, and is determined according to the distillation temperature. If the distillation pressure is high, the boiling point of ⁇ -myrcene will rise and the distillation temperature will also rise, so dimerization of ⁇ -myrcene occurs in the same manner as in the case of the high distillation temperature described above, and the yield of ⁇ -myrcene decreases, which is disadvantageous. .
  • Polymerization inhibitors include TBC (tertiary butylcatechol), BHT (dibutylhydroxytoluene), benzoquinone, hydroquinone, and the like.
  • the amount to be added is preferably 1% by weight or less, more preferably 0.5% by weight or less, and still more preferably 0.1% by weight based on the weight of the ⁇ -myrcene raw material composition from the viewpoint of the purity of the purified product. 10 ppm or more is preferable from the viewpoint of expression of the effect of the polymerization inhibitor.
  • the ⁇ -myrcene composition according to the present embodiment can be obtained as a polymer by using the ⁇ -myrcene composition according to the present embodiment, an aromatic vinyl hydrocarbon-based monomer, and a conjugated diene-based monomer other than ⁇ -myrcene as polymerization raw materials. .
  • the resulting polymer even if it is a ⁇ -myrcene polymer composed of ⁇ -myrcene monomer units, is composed of ⁇ -myrcene monomer units and aromatic vinyl hydrocarbon-based monomer units or aromatic vinyl hydrocarbon-based monomer units and other than ⁇ -myrcene monomer units. It may be a copolymer (P) containing conjugated diene-based monomer units.
  • the monomer units contained in the copolymer (P) according to this embodiment are described below.
  • the aromatic vinyl hydrocarbon-based monomer unit is a structural unit of the copolymer derived from the aromatic vinyl hydrocarbon-based monomer used for copolymerization.
  • aromatic vinyl hydrocarbon monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene and ⁇ -methylstyrene. , ⁇ -methyl-p-methylstyrene and the like.
  • These aromatic vinyl hydrocarbon monomers may be used alone or in combination of two or more.
  • a conjugated diene is a constituent unit of a copolymer derived from a conjugated diene-based monomer used for copolymerization.
  • conjugated diene-based monomers include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3- hexadiene, farnesene and the like. These conjugated diene-based monomers may be used alone or in combination of two or more.
  • Copolymer (P) containing ⁇ -myrcene monomer units and aromatic vinyl hydrocarbon-based monomer units according to the present embodiment, ⁇ -myrcene monomer units, aromatic vinyl hydrocarbon-based monomer units, and conjugated diene-based monomers other than ⁇ -myrcene
  • the copolymer (P) containing units may be a block copolymer containing polymer blocks containing ⁇ -myrcene monomer units.
  • the "polymer block containing ⁇ -myrcene monomer units" of the copolymer (P) of the present embodiment means that 80 to 100 mass of ⁇ -myrcene monomer units are contained in 100% by mass of the polymer block containing ⁇ -myrcene monomer units. %, more preferably 90 to 100% by mass of ⁇ -myrcene monomer units. Specifically, it may be, for example, 80, 85, 90, 95, or 100% by mass, and may be within a range between any two of the numerical values exemplified here. Also, the block containing ⁇ -myrcene monomer units may be a block containing substantially only ⁇ -myrcene monomer units.
  • the "polymer block containing ⁇ -myrcene monomer units" in the present embodiment contains 0 to 20% by mass of monomer units other than ⁇ -myrcene monomer units in 100% by mass of the polymer block containing ⁇ -myrcene monomer units.
  • Monomer units other than such ⁇ -myrcene monomer units are monomer units derived from impurities contained in ⁇ -myrcene, for example, monomer units derived from terpene oxide and monomer units derived from dimers of ⁇ -myrcene. mentioned.
  • the "polymer block containing ⁇ -myrcene monomer units" in the present embodiment may contain monomer units other than ⁇ -myrcene monomer units and monomer units derived from impurities contained in ⁇ -myrcene.
  • the unit content is preferably less than 20% by mass, more preferably less than 10% by mass, based on 100% by mass of polymer blocks containing ⁇ -myrcene monomer units.
  • the content of the ⁇ -myrcene monomer unit in the polymer block containing the ⁇ -myrcene monomer unit can be adjusted, for example, by adjusting the content of the ⁇ -myrcene monomer contained in the ⁇ -myrcene composition, Adjusting the ratio of the ⁇ -myrcene composition with respect to the total amount added when other monomers are added to the reaction system at once, It can be controlled by controlling the supply flow rate or the like.
  • the polymer of the present embodiment is obtained by polymerizing monomers by a known polymerization method, examples of which include anionic polymerization, cationic polymerization, and living radical polymerization. Anionic polymerization is preferred from the viewpoint of structural control of the copolymer.
  • the ⁇ -myrcene composition and the aromatic vinyl hydrocarbon-based monomer to be copolymerized, or the ⁇ -myrcene composition, the aromatic vinyl hydrocarbon-based monomer, and the conjugated diene-based monomer are added to the reaction system all at once.
  • ⁇ Method for producing block copolymer> In order to obtain a block copolymer by including a polymer block containing a ⁇ -myrcene monomer unit in the copolymer (P), for example, the content of the ⁇ -myrcene monomer in the total monomers added to the reaction system is 80 mass. % or more of the polymerization monomer is added to the reaction system and polymerized for a predetermined period of time. For example, the polymerization monomer is continuously supplied to the reaction system for a certain period of time. In one embodiment, polymer blocks containing ⁇ -myrcene monomer units can be included in the copolymer (P) by adding only the ⁇ -myrcene composition to the reaction system and polymerizing for a predetermined period of time.
  • a block copolymer containing polymer blocks can be obtained by performing the following steps (A) to (C) in any order and any number of times.
  • some steps may not be performed.
  • step (B) it is possible to include polymer blocks containing ⁇ -myrcene monomer units in the copolymer (P).
  • step (D) may be performed between steps (A) to (C).
  • a step of adding an aromatic vinyl hydrocarbon-based monomer to the reaction system and polymerizing the aromatic vinyl hydrocarbon-based monomer for a predetermined time (B) Adding a ⁇ -myrcene composition to the reaction system to obtain a predetermined amount of ⁇ -myrcene (C) adding a conjugated diene-based monomer other than ⁇ -myrcene to the reaction system and polymerizing the conjugated diene-based monomer for a predetermined time (D) adding a ⁇ -myrcene composition and an aromatic vinyl hydrocarbon to the reaction system; A step of adding a mixture containing a monomer and at least two or more of conjugated diene monomers other than ⁇ -myrcene, and polymerizing the monomers contained in the mixture.
  • n-butyl lithium n-butyl lithium, 10% by mass cyclohexane solution (trade name), Styrene (trade name) manufactured by Albemarle, 1,3-butadiene (trade name) manufactured by Denka, Chiba Butadiene Kogyo Co., Ltd.
  • a ⁇ -myrcene raw material composition was prepared as a purchased product, and 0.05 part by weight of BHT (dibutylhydroxytoluene) was mixed with 100 parts by weight of the ⁇ -myrcene raw material composition to prepare a raw material for distillation.
  • BHT dibutylhydroxytoluene
  • Example 1 The starting material was continuously supplied from the bottom to the fifth stage of the first column (10 theoretical plates, distillation pressure of 10 kPaA, reflux ratio of 0.1, kettle temperature of 93° C.) at a flow rate of 100 g/h.
  • the first column 1.0 g/h was continuously withdrawn from the top of the column.
  • the bottom liquid of the first tower was sent to the second tower.
  • the bottom liquid of the first column was continuously supplied to the fifth column from the bottom of the second column (10 theoretical plates, distillation pressure of 10 kPaA, reflux ratio of 2.0, pot temperature of 109°C).
  • Example 2 The starting material was continuously supplied from the bottom to the fifth stage of the first column (10 theoretical plates, distillation pressure of 10 kPaA, reflux ratio of 0.1, kettle temperature of 93° C.) at a flow rate of 100 g/h.
  • 1.0 g/h was continuously withdrawn from the top of the column.
  • the bottom liquid of the first tower was sent to the second tower.
  • the bottom liquid of the first column was continuously supplied to the fifth column from the bottom of the second column (10 theoretical plates, distillation pressure of 10 kPaA, reflux ratio of 1.0, kettle temperature of 122°C).
  • Example 3> The starting material was continuously supplied to the first column (10 theoretical plates, distillation pressure 5 kPaA, reflux ratio 0.1, kettle temperature 76° C.) from the bottom to the fifth column at a flow rate of 100 g/h. In the first column, 1.0 g/h was continuously withdrawn from the top of the column. The bottom liquid of the first tower was sent to the second tower. The bottom liquid of the first column was continuously supplied to the fifth column from the bottom of the second column (10 theoretical plates, distillation pressure 5 kPaA, reflux ratio 0.1, kettle temperature 101° C.).
  • Example 4 The starting material was continuously supplied to the fifth stage from the bottom of the first column (10 theoretical stages, distillation pressure 60 kPaA, reflux ratio 0.5, kettle temperature 143° C.) at a flow rate of 100 g/h. In the first column, 1.0 g/h was continuously withdrawn from the top of the column. The bottom liquid of the first tower was sent to the second tower. The bottom liquid of the first column was continuously supplied to the fifth column from the bottom of the second column (10 theoretical plates, distillation pressure 60 kPaA, reflux ratio 1.0, kettle temperature 148° C.).
  • Example 5 The raw material was continuously supplied directly to the second column (10 theoretical plates, distillation pressure 5 kPaA, reflux ratio 1.0, pot temperature 110° C.) at a flow rate of 100 g per hour. In the second column, 4.4 g/h was continuously withdrawn from the bottom of the column, and 95.6 g/h was recovered as a ⁇ -myrcene composition from the top of the column. The purity of ⁇ -myrcene in the resulting ⁇ -myrcene composition was 85.4%. Table 1 shows the analysis results of the resulting ⁇ -myrcene composition.
  • Example 6> The starting material was continuously supplied from the bottom to the fifth stage of the first column (10 theoretical plates, distillation pressure of 10 kPaA, reflux ratio of 1.0, pot temperature of 93° C.) at a flow rate of 100 g/h. In the first column, 0.5 g/h was continuously withdrawn from the top of the column. The bottom liquid of the first tower was sent to the second tower. The bottom liquid of the first column was continuously supplied to the fifth column from the bottom of the second column (10 theoretical plates, distillation pressure 10 kPaA, reflux ratio 0.1, kettle temperature 121° C.).
  • Example 7 1000 g of raw material was placed in a 3000 mL three-necked flask equipped with a distillation column with 10 theoretical plates. Distillation was carried out under conditions of a pot temperature of 95° C., a distillation pressure of 10 kPaA, and no reflux, and after removing 50 g of the initial distillation, 820 g of a ⁇ -myrcene composition was recovered as a distillate. 130 g of residue remained in the flask. The purity of ⁇ -myrcene in the obtained ⁇ -myrcene composition was 82.6%. Table 2 shows the analysis results of the resulting ⁇ -myrcene composition.
  • Example 9 1000 g of raw material was placed in a 3000 mL three-necked flask equipped with a distillation column with 10 theoretical plates. Distillation was carried out under conditions of a kettle temperature of 160°C, a distillation pressure of 85 kPaA, and no reflux. After 50 g of initial distillation was removed, distillation stopped when 530 g was distilled. The distillate obtained so far was obtained as a ⁇ -myrcene composition. The purity of ⁇ -myrcene in the obtained ⁇ -myrcene composition was 83.3%. Table 2 shows the analysis results of the resulting ⁇ -myrcene composition.
  • ⁇ Comparative Example 2 1000 g of raw material was placed in a 3000 mL three-necked flask equipped with a distillation column with 10 theoretical plates. Distillation was carried out under conditions of a kettle temperature of 95° C., a distillation pressure of 10 kPaA, and no reflux, and after removing 10 g of the initial distillation, 975 g of a ⁇ -myrcene composition was recovered as a distillate. 15 g of residue remained in the flask. The purity of ⁇ -myrcene in the resulting ⁇ -myrcene composition was 73.8%. Table 2 shows the analysis results of the resulting ⁇ -myrcene composition.
  • GC gas chromatography
  • ⁇ -myrcene and substance groups 1 to 4 The peaks of ⁇ -myrcene and substance groups 1 to 4 in the chromatogram obtained from gas chromatography (GC) measurement were identified and determined as follows. (1) ⁇ -myrcene In the chromatogram obtained by gas chromatography analysis under the above conditions, the maximum peak appearing at a retention time of approximately 16 to 17 minutes is highly likely to be derived from ⁇ -myrcene. The largest peak appearing at the retention time of 16-17 minutes was identified as originating from ⁇ -myrcene by gas chromatograph-mass spectrometry.
  • Substance group 2 The retention time of the ⁇ -myrcene peak identified as described above is defined as a relative retention time of 1.0, and peaks appearing in the range of relative retention times of 1.10 to 1.29 are defined as substance group 2 peaks. determined.
  • Substance group 3 The retention time of the ⁇ -myrcene peak identified as described above is defined as a relative retention time of 1.0, and peaks appearing in the range of relative retention times of 1.78 to 2.45 are defined as substance group 3 peaks. determined.
  • Substance group 4 The retention time of the ⁇ -myrcene peak identified as described above is defined as a relative retention time of 1.0, and the peaks appearing in the range of relative retention times of 0.00 to 0.49 are defined as the peaks of Substance Group 4. determined.
  • ⁇ Polymerization of ⁇ -myrcene composition > ⁇ Polymerization Example 1> 500.0 g of cyclohexane and 75.0 mg of tetrahydrofuran (THF) were added into a reaction vessel equipped with a stirrer. 2.5 mL of a 10% by mass cyclohexane solution of n-butyllithium was added to the mixture as a polymerization initiator solution, and the mixture was kept at 30.degree.
  • THF tetrahydrofuran
  • Example 2 214.6 g of the ⁇ -myrcene composition obtained in Example 1 was added thereto, ⁇ -myrcene was anionically polymerized, and the polymerization active terminals were deactivated with water to obtain a polymerization solution containing a ⁇ -myrcene polymer. This polymerization solution was devolatilized to obtain a ⁇ -myrcene polymer.
  • the weight average molecular weight (Mw) of the ⁇ -myrcene polymer was 85,000. Table 3 shows the analysis results of the obtained ⁇ -myrcene polymer.
  • ⁇ Polymerization Example 2 500.0 g of cyclohexane and 75.0 mg of tetrahydrofuran (THF) were added into a reaction vessel equipped with a stirrer. 2.5 mL of a 10% by mass cyclohexane solution of n-butyllithium was added to the mixture as a polymerization initiator solution, and the mixture was kept at 30.degree. 233.4 g of the ⁇ -myrcene composition obtained in Example 2 was added thereto, ⁇ -myrcene was anionically polymerized, and the polymerization active terminals were deactivated with water to obtain a polymerization solution containing a ⁇ -myrcene polymer.
  • THF tetrahydrofuran
  • This polymerization solution was devolatilized to obtain a ⁇ -myrcene polymer.
  • the weight average molecular weight (Mw) of the ⁇ -myrcene polymer was 89,000.
  • Table 3 shows the analysis results of the obtained ⁇ -myrcene polymer.
  • THF tetrahydrofuran
  • This polymerization solution was devolatilized to obtain a ⁇ -myrcene polymer.
  • the ⁇ -myrcene polymer weight average molecular weight (Mw) was 99,000.
  • Table 3 shows the analysis results of the obtained ⁇ -myrcene polymer.
  • THF tetrahydrofuran
  • This polymerization solution was devolatilized to obtain a ⁇ -myrcene polymer.
  • the weight average molecular weight (Mw) of the resulting poly- ⁇ -myrcene polymer was 97,000. 3 shows the analysis results of the obtained ⁇ -myrcene polymer.
  • THF tetrahydrofuran
  • This polymerization solution was devolatilized to obtain a ⁇ -myrcene polymer.
  • the weight average molecular weight (Mw) of the ⁇ -myrcene polymer was 113,000.
  • Table 3 shows the analysis results of the obtained ⁇ -myrcene polymer.
  • THF tetrahydrofuran
  • This polymerization solution was devolatilized to obtain a ⁇ -myrcene polymer.
  • the weight average molecular weight (Mw) of the ⁇ -myrcene polymer was 135,000.
  • Table 3 shows the analysis results of the obtained ⁇ -myrcene polymer.
  • THF tetrahydrofuran
  • This polymerization solution was devolatilized to obtain a ⁇ -myrcene polymer.
  • the weight average molecular weight (Mw) of the ⁇ -myrcene polymer was 88,000.
  • Table 4 shows the analysis results of the obtained ⁇ -myrcene polymer.
  • THF tetrahydrofuran
  • This polymerization solution was devolatilized to obtain a ⁇ -myrcene polymer.
  • the weight average molecular weight (Mw) of the ⁇ -myrcene polymer was 126,000.
  • Table 4 shows the analysis results of the obtained ⁇ -myrcene polymer.
  • ⁇ Polymerization Example 9 500.0 g of cyclohexane and 75.0 mg of tetrahydrofuran (THF) were added into a reaction vessel equipped with a stirrer. 2.5 mL of a 10% by mass cyclohexane solution of n-butyllithium was added to the mixture as a polymerization initiator solution, and the mixture was kept at 30.degree. 240.1 g of the ⁇ -myrcene composition obtained in Example 9 was added thereto, ⁇ -myrcene was anionically polymerized, and the polymerization active terminals were deactivated with water to obtain a polymerization solution containing a ⁇ -myrcene polymer.
  • THF tetrahydrofuran
  • This polymerization solution was devolatilized to obtain a ⁇ -myrcene polymer.
  • the weight average molecular weight (Mw) of the ⁇ -myrcene polymer was 95,000.
  • Table 4 shows the analysis results of the obtained ⁇ -myrcene polymer.
  • THF tetrahydrofuran
  • the ⁇ -myrcene composition 25 obtained in Example 1 was obtained. .8 g was added to anionically polymerize the ⁇ -myrcene. The internal temperature rose to 58°C. After lowering the internal temperature of the reaction system to 50° C., sampling a small amount of the reaction solution and confirming that 95% by mass or more of the added ⁇ -myrcene was consumed by GC measurement, 36.0 g of 1,3-butadiene was added. , 1,3-butadiene was anionically polymerized.
  • the internal temperature of the reaction system was lowered to 50° C., a small amount of the reaction solution was sampled, and after confirming that 95% by mass or more of the added 1,3-butadiene had been consumed by GC measurement, 110.0 g of styrene was added for the second time. was added to complete the polymerization.
  • the polymerization active terminal was deactivated with water to obtain a polymerization liquid containing the block copolymer.
  • This polymerization solution was devolatilized to obtain a block copolymer.
  • the weight average molecular weight (Mw) of the block copolymer was 78,000. Table 5 shows the analysis results of the obtained block copolymer.
  • THF tetrahydrofuran
  • This polymerization solution was devolatilized to obtain a ⁇ -myrcene polymer.
  • the weight average molecular weight (Mw) of the ⁇ -myrcene polymer was 162,000.
  • Table 3 shows the analysis results of the obtained ⁇ -myrcene polymer.
  • THF tetrahydrofuran
  • This polymerization solution was devolatilized to obtain a ⁇ -myrcene polymer.
  • the weight average molecular weight (Mw) of the ⁇ -myrcene polymer was 221,000.
  • Table 4 shows the analysis results of the obtained ⁇ -myrcene polymer.
  • THF tetrahydrofuran
  • the internal temperature of the reaction system was lowered to 50° C., 28.7 g of the ⁇ -myrcene composition obtained in Comparative Example 1 was added, and ⁇ -myrcene was anionically polymerized.
  • the internal temperature rose to 55°C.
  • sampling a small amount of the reaction solution and confirming that 95% by mass or more of the added ⁇ -myrcene was consumed by GC measurement 36.0 g of 1,3-butadiene was added. , 1,3-butadiene was anionically polymerized.
  • the internal temperature rose to 64°C.
  • the internal temperature of the reaction system was lowered to 50° C., a small amount of the reaction solution was sampled, and after confirming that 95% by mass or more of the added 1,3-butadiene had been consumed by GC measurement, 110.0 g of styrene was added for the second time. was added to complete the polymerization. Finally, the polymerization active terminal was deactivated with water to obtain a polymerization liquid containing the block copolymer. This polymerization solution was devolatilized to obtain a block copolymer. The weight average molecular weight (Mw) of the block copolymer was 118,000. Table 5 shows the analysis results of the obtained block copolymer.
  • the weight average molecular weight (Mw) of the ⁇ -myrcene polymer and copolymer (P) is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • ⁇ Evaluation of obtained ⁇ -myrcene polymer> The ⁇ -myrcene polymers obtained in Polymerization Examples 1 to 9 and Comparative Polymerization Examples 1 to 3 were evaluated based on the following evaluation criteria.
  • the weight-average molecular weight of the ⁇ -myrcene polymer is 140,000 or more (the weight-average molecular weight at which the initiator efficiency is less than 49%)
  • the copolymer (P) obtained in Polymerization Example 10 was evaluated based on the following evaluation criteria.
  • the ⁇ -myrcene compositions according to the examples had improved initiator efficiency during anionic polymerization, and ⁇ -myrcene-containing polymers having the desired weight-average molecular weight were obtained. It is understood. On the other hand, it is understood that the ⁇ -myrcene composition according to the comparative example cannot yield a ⁇ -myrcene-containing polymer having the desired molecular weight when anionic polymerization is carried out with the same amount of catalyst as in the example.
  • the purified ⁇ -myrcene composition according to the present invention has a low content of polymerization inhibitors and an improved initiator efficiency during anionic polymerization.
  • the ⁇ -myrcene composition according to the present invention has industrial applicability as an anionically polymerizable ⁇ -myrcene.

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Abstract

L'invention concerne une composition de bêta-myrcène à faible teneur en inhibiteur de polymérisation et dans laquelle l'efficacité de l'initiateur dans une polymérisation anionique est augmentée, ainsi qu'un procédé de production de polymère mettant en oeuvre cette composition de bêta-myrcène. Plus spécifiquement, selon l'invention et pour cette composition de bêta-myrcène, dans une analyse par chromatographie en phase gazeuse dans les conditions ci-dessous, le rapport de surface de pic du bêta-myrcène est supérieur ou égal à 75%, et lorsque le temps relatif de rétention de ce pic du bêta-myrcène est 1,0, alors le rapport de surface de pic d'un groupe de substances 1 pour lesquelles le temps relatif de rétention est compris dans la plage 1,29 à 1,78, est inférieur ou égal à 1000 ppm. Conditions de l'analyse par chromatographie en phase gazeuse: colonne utilisée: DB-1, fabrication Agilent Technologies; phase stationnaire: diméthylpolysiloxane; diamètre intérieur: 0,32 mm; longueur: 50,0 m; épaisseur de film: 0,52 μｍ, condition d'augmentation de la température: 60℃, 12 minutes de maintien, augmentation de 10℃ par minute jusqu'à 300℃, 12 minutes de maintien, temps d'augmentation de la température 24 minutes, total 48 minutes; température à l'orifice d'injection: 280℃; pression à l'orifice d'injection: 169,2 kPa; gaz vecteur: hélium; débit de la colonne: 4,0 mL/min.; taux de séparation: 20; quantité injectée: 0,5 μL; introduction de la composition de bêta-myrcène telle quelle; détecteur: FID; température de détection: 300℃.
PCT/JP2022/019596 2021-05-25 2022-05-06 Composition de bêta-myrcène ainsi que procédé de production de polymère mettant en oeuvre cette composition de bêta-myrcène WO2022249866A1 (fr)

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CN102701981A (zh) * 2012-06-29 2012-10-03 太仓市新星轻工助剂厂 增塑剂4-(4-甲基-3-戊烯基)-4-环己烯-1，2-酸异辛酯的合成方法
CN102718674A (zh) * 2012-06-15 2012-10-10 中国林业科学研究院林产化学工业研究所 一种月桂烯基酰胺及其合成方法和应用
CN114324657A (zh) * 2021-12-29 2022-04-12 浙江大学 一种吹扫捕集与gc-ms相结合土壤中月桂烯检测方法

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JP6164927B2 (ja) * 2013-05-16 2017-07-19 住友ゴム工業株式会社 空気入りタイヤ
JP6159574B2 (ja) * 2013-05-16 2017-07-05 住友ゴム工業株式会社 分枝共役ジエン共重合体および水添分枝共役ジエン共重合体、ゴム組成物、並びに空気入りタイヤ
US10053603B2 (en) * 2014-04-02 2018-08-21 Kraton Polymers U.S. Llc Block copolymers containing a copolymer myrcene block
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CN102718674A (zh) * 2012-06-15 2012-10-10 中国林业科学研究院林产化学工业研究所 一种月桂烯基酰胺及其合成方法和应用
CN102701981A (zh) * 2012-06-29 2012-10-03 太仓市新星轻工助剂厂 增塑剂4-(4-甲基-3-戊烯基)-4-环己烯-1，2-酸异辛酯的合成方法
CN114324657A (zh) * 2021-12-29 2022-04-12 浙江大学 一种吹扫捕集与gc-ms相结合土壤中月桂烯检测方法

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